JPS6257646B2 - - Google Patents

Abstract

The method of hardening a glycidyl compound with a polyether urethane urea amino hardener is disclosed, said hardener being prepared by reacting (1) a blocked prepolymer prepared by reacting a phenolic compound with the reaction product of a polyether polyol with an excess of polyisocyanate, with (2) a polyfunctional amino compound.

Description

[Detailed description of the invention]

The subject of the present invention is prepolymer carbamic acid aryl esters and difunctional or polyfunctional amine compounds having more than one reactive hydrogen atom per molecule and on average more than one epoxide group per molecule. A curable plastic mixture consisting of a glycidyl compound having the following properties: Plastics based on epoxide resins cured with polyamines are in fact characterized by a series of desirable properties, such as good adhesion strength to organic and inorganic substrates, good solvent stability, high resistance to chemicals, etc. It will be done. Because of their high network density, amine-cured epoxide resins, especially those based on diphenylpropane and epichlorohydrin, have brittle hardness in the glass transition range above 20°C. However, these plastics still do not meet the practical requirements in all fields of use where impact strength as well as high flexibility are required. This is particularly true for building components, for example, where it is required to permanently eliminate shrinkage cracks in concrete. The elasticity can be increased internally to a certain extent by reducing the reticulation density, and the elasticity can be increased externally by adding softeners. External elastomers such as tars, phthalates, high boiling alcohols, vinyl polymers and the like are non-reactive and cannot be incorporated into the cured resin lattice. They only expand by filling space. Internal elasticity can be obtained by reducing the functionality of the curing agent. Long-chain, low-functionality aminoamides based on dimerized resin acids, which have been used extensively for many years, yield satisfactory properties as flexible hardeners for epoxide resins, but in certain areas It cannot be used as desired. German Patent Application No. 21 52 606 describes curable plastic mixtures consisting of a certain glycidyl ethers, b certain carbamic acid phenyl esters consisting of prepolymer isocyanates and alkyl phenols, and c polyamines or polyaminoamides. has been done. However, mixtures of carbamic acid phenyl esters and epoxide resins have final viscosities which are actually too high due to the high viscosities of the individual components. Diluents must therefore be added to produce a usable mixture. Another problem is that because the equivalent weights of the resin and hardener components are significantly different, significantly more resin components (epoxide + polyurethane) must be mixed with only a small amount of hardener, and the resin
Homogenization is not easy at all due to poor mixing properties due to the difference in viscosity of the curing agent components, and caution is required. According to DE 23 38 256 A1, polymeric amine trimerized polyether urethane ureas are prepared by reacting prepolymers containing free isocyanate groups with amines in highly dilute solution. and then cured with epoxide resin. Although the use of solvents, especially aromatic solvents, has practical disadvantages from an industrial and health point of view and is therefore undesirable, it is essential for the process described above. This is because otherwise gelation would occur. Furthermore, the viscosity of the solvent-free reaction product, which is purposefully prepared according to DE 23 38 256 A1, is too high for practical use. German Patent Application No. 2418041 describes a method for producing elasticized molded bodies and surface-forming bodies, in which specific epoxide compounds are added by hydrolysis of specific prepolymer ketimines or enamines. React with the resulting amine compound. In this way it is possible to produce cured resins with improved properties that are resistant to chemicals and can be maintained well. However, upon hydrolysis of the above compounds, ketones or aldehydes are liberated,
These must be removed. Furthermore, it is desirable to further improve the elasticity of the cured product. The object of the present invention is to overcome these disadvantages and to provide coatings, adhesives, surface-forming agents, packing agents which are resistant to chemicals, have good adhesion, have high impact strength and improved flexibility. The object of the invention is to obtain a curable plastics mixture which gives rise to shaped bodies. This problem is solved according to the invention by: A polyether urethane urea amine having two or more reactive amine hydrogens per molecule, which consists of: 1 difunctional or polyfunctional carbamic acid aryl ester; 2 at least one difunctional and/or polyfunctional amine compounds, which a contain at least two reactive amine hydrogens in one molecule, or b contain at least one reactive amine hydrogen in one molecule and at least (containing one azomethine group), and the amine is liberated from the reaction product of 1 and 2b by subsequent hydrolysis of the azomethine group]
and B glycidyl compounds having on average more than one epoxide group per molecule and optionally C customary fillers, pigments, reaction promoters, viscosity modifiers and additives, The solution is a curable plastic mixture. Embodiments of the invention are set out in claims 2 and 3. The amine components used together according to claim 1A are 1A1 difunctional or polyfunctional coupled aliphatic isocyanates, 1A2a at least one difunctional difunctional isocyanate having two active amine hydrogen atoms per molecule. It is prepared by reacting with an excess of a functional and/or polyfunctional amine compound and/or with an amine compound having at least one reactive amine hydrogen and at least one azomethine group per molecule of A2b. Compounds containing di- or polyfunctional coupled isocyanates which can be used together according to claim 1 A1) include linear or branched hydroxyl groups and A polyalkylene polyether polyol and/or a polyalkylene thioether polyol containing a sulfhydrin group is reacted with a di- or polyisocyanate (NCO/OH
(SH)-ratio 1.5 to 2.5), it is possible to use the reaction product obtained by subsequently reacting the unterminated NCO group with a coupling agent customary in this field (German Patent Application No. 2152606). Specification). Linear or branched polyol components having an average molecular weight of from 150 to 10,000 include polyalkylene polyether polyols, which combine, for example, alkylene oxides, especially ethylene oxide, propylene oxide with difunctional or polyfunctional alcohols such as ethanediol-(1, 2), propanediol-(1,
3) Butanediol-(1,4) and especially higher functionality alcohols such as 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerin, 1,2,6-hexanetriol or by copolymerization, block copolymerization or anionic polymerization with amines such as ethylene diamine and 1,6-hexamethylene diamine as initiators, or by cationic polymerization of cyclic ethers such as tetrahydrofuran, ethylene oxide and propylene oxide with acidic catalysts. and by copolymerization and by polycondensation of polycondensable glycols such as hexanediol-(1,6) in the presence of acidic etherification catalysts. Polyalkylenethioether polyols include thiodiglycol itself and diols and/or polyols such as hexanediol.
(1,6), triethylene glycol, 2,2-dimethyl-propanediol-(1,3) and 1,
Acidic etherification catalysts such as polycondensation products with 1,1-trimethylolpropane in the presence of phosphoric acid and phosphorous acid are mentioned. Examples of polyacetals include formaldehyde and diols and/or polyols such as diethylene glycol, triethylene glycol, butanediol (1,4), hexanediol (1,
6), thiodiglycol and 1,1,1-trimethylolpropane and an acidic catalyst such as phosphoric acid and p-
Examples include polycondensation products with triolsulfonic acid. Other polyol components include compounds containing reactive multiple bonds, and polyhydroxyl and sulfhydryl components such as polyisobutylene diols, polyisoprene diols, and corresponding addition products consisting of compounds containing SH groups in the terminal positions. (See US Pat. No. 3,984,370). The hydroxyl or sulfhydryl component is reacted in a known manner with a di- or polyfunctional isocyanate at an NCO/CH ratio of 1.5 to 2.5, preferably 1.8 to 2.2, in a manner known per se to obtain NCO at the terminal position.
yielding a prepolymer compound having groups. Suitable polyisocyanates include, for example: 1,6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 2,4,4-(2,
2,4)-trimethyl-1,6-diisocyanate-hexane, 1-methyl-2,4-(2,6)-
Diisocyanate - cyclohexane, methylene -
Bis(4-cyclohexyl isocyanate), an isocyanate produced from a dimeric fatty acid diamine by a conventional method. The unterminated NCO groups of the di- or polyfunctional prepolymer compound are then combined with at least a stoichiometric amount of coupling agents customary in the field from 50 to 120%.
The reaction is carried out at a temperature of °C, optionally in the presence of a catalyst. Coupling agents include phenols and alkylphenols, which may be substituted by alkyl groups having from 1 to 18 carbon atoms, such as butylphenol, tetramethylbutylphenol,
Mixtures of amylphenol, hexylphenol, heptylphenol and especially 4-nonylphenol can be used advantageously. Difunctional and/or polyfunctional amine compounds that can be used for other reactions in Claim 1 A2 include di-primary, di-secondary and monofunctional amine compounds.
Examples include class/secondary aliphatic, alicyclic, heterocyclic, and araliphatic amines and their condensation products with carboxylic acids (polyaminoamides). These amines, which may optionally be substituted and have at least two active amine hydrogens in one molecule, are combined with an amino group/coupled NCO group ratio of 1.5 to 2.5, preferably 1.8 to 2.2. ~100℃, advantageously
The corresponding prepolymeric amine compounds can be produced alone or in mixtures by reaction with components containing carbamic acid aryl ester groups at temperatures of 60 DEG to 80 DEG C. It is also possible to use larger amounts of the amine component and remove the excess after the reaction has ended, for example by distillation.
Phenol components liberated during the reaction may remain in the reaction mixture. In the present invention, one or more of the following compounds are used as the amine compound; α General formula: R-NH-R ¹ -NH-R () [wherein R is a straight or branched alkyl having 1 to 4 carbon atoms] R ¹ represents an optionally substituted aromatic aliphatic or alicyclic alkyl group having 2 to 20 carbon atoms, especially 1,2-diaminopropane, or a dimeric diamine alkyl group. and/or optionally interrupted by a heteroatom, in particular an oxygen atom,
and/or β General formula: R ² −(R ³ −NH−) _n −R ³ −R ² () [In the formula, R ² is

[Formula], R ³ represents −CH ₂ −CH ₂ − and/or −CH ₂ −CH ₂ −CH ₂ −, R ⁴ may be the same or different, and −
CH ₃ , −CH ₂ −CH ₃ ,

[Formula], m represents 1 or 2], and/or γ General formula: [In the formula, R ⁵ is a hydrogen atom or -(CH ₂ ) _k -R ² (k
=2 or 3), or

[Formula] represents (R ⁶ = - NHR or R ² , h = 0, 1, 2, 3),
and/or δ ^where
When using an amine of the formula = R ² , the ratio of amino group: carbamic acid aryl ester group is 1:1, and the amine of the formula m = 2 and the amine of the formula,
When using an amine with the formula R ⁶ = -NHR, the ratio of amino group: carbamic acid aryl ester group is 1.8:1 to 2:1, and the amino group is released by hydrolysis from the compound containing the group R ² . Examples of polyamines that can be used in the invention include: ethylenediamine, diethylenetriamine,
1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, 3-(n-isopropyl-amino)
Propylamine, hexapropyleneheptamine,
1-cyclohexylamino-3-aminopropane, 1,4-diaminocyclohexane, 1,3-
Diaminocyclohexane, 2,4-diaminocyclohexane, 1,3-di(amino-cyclohexyl)propane, N,N'-diethyl-1,3-diaminopropane, N,N-diethyl-1,4-diaminocyclohexane, N -aminoethylpiperazine, N-aminopropylpiperazine, N-aminobutylpiperazine, 1,3-dipiperazinylpropane, 1,3-dipiperidylpropane, 3-
(2-aminoethyl)-aminopropylamine,
N,N'-bis-(3-aminopropyl)-ethylenediamine, commercially available customary primary aliphatic polyoxypropylene di- or triamines, phenylenediamine, 4,4'-diamino-diphenylmethane and ether diamines such as 1, 7-diamino-4
-oxaheptane, 1,7-diamino-3,5
-dioxa-heptane, 1,10-diamino-4,
7-dioxa-decane, 1,10-diamino-4,
7-dioxa-5-methyldecane, 1,11-diamino-6-oxaundecane, 1,11-diamino-4,8-dioxaundecane, 1,11-diamino-4,8-dioxa-5-methyl-undecane , 1,11-diamino-4,8-dioxa-5,
6-dithymel-7-propionyl-undecane,
1,12-diamino-4,9-dioxa-dodecane, 1,13-diamino-4,10-dioxatridecane, 1,13-diamino-4,7,10-trioxa-5,8-dimethyl-tridecane , 1,14-diamino-4,11-dioxa-tetradecane, 1,
14-diamino-4,7,10-trioxatetradecane, 1,16-diamino-4,7,10,13-tetraoxa-hexadecane, 1,20-diamino-
4,17,-dioxa-eicosane and especially hexamethylene diamine, 3,3,5(3,5,5)-
Trimethylhexamethylenediamine and 3,3'-
Dimethyl-4,4'-diaminodicyclohexylmethane and especially isophorone diamine, N-aminoethylpiperazine, 1,2-diaminopropane, methyl-pentamethylene diamine, xylylene diamine or mixtures of these amines. The polyaminoamides used together according to the invention are dicarboxylic acids such as succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylene dicarboxylic acid,
It is a condensation product from decamethylene dicarboxylic acid, a dicarboxylic acid obtained by carbonylating an unsaturated fatty acid and an excess of amine, such as the compounds mentioned above. Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, myristic acid, palmitic acid,
polyaminoamides and imidazoline group-containing polyaminoamides based on monocarboxylic acids such as oil acids, linoleic acid, linolenic acid, and natural animal and vegetable fatty acids and their esters;
and the polyamines mentioned above, especially polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, can likewise be used alone or in mixed form. Amides preferred according to the invention are polyaminoamides based on dimerized fatty acids and an excess of polyalkylene polyamines and polyaminoamides containing imidazoline groups, which belong to the state of the art known in the field of epoxide resins as curing agents. or a mixture thereof with the above amines. For further modifications of the hardeners according to claim 1A which are advantageous in the invention described above, it is also possible to use together the amine hardeners for epoxide resins which are customary in this field. The epoxide resins according to claim 1B with which they are used according to the invention can be cured with these hardeners or hardener mixtures by heating and cooling. These resins contain on average more than one epoxide group per molecule and contain polyhydric alcohols such as glycerin, glycidyl ether of hydrogenated diphenylolpropane,
Alternatively, it is also possible to use glycidyl esters of polyhydric carboxylic acids such as hexahydrophthalic acid or dimerized fatty acids, which may be glycidyl ethers of polyhydric phenols such as resorcinol, diphenylolpropane or phenol-aldehyde condensates. can. The epoxide value of the above compounds is approximately 0.2~
It is 0.7. Particular preference is given to using liquid epoxide resins based on epichlorohydrin and diphenylpropane with a molecular weight of 340 to 450. Optionally, monofunctional epoxide compounds can be used to reduce the viscosity of the mixture and thereby improve processability. Examples of this are aliphatic and aromatic glycidyl ethers, such as butyl glycidyl ether, phenyl glycidyl ether or glycidyl esters, such as glycidyl acrylate or epoxides such as styrene oxide. For shaping or casting the reactive composition for coating, adhesion, the customary fillers, pigments, softeners, accelerators, based on minerals and organics, are used.
Other solvents and other additives commonly used in the epoxide resin field are used. The curable mixtures according to the invention are used as coatings, adhesives, surfacing agents, packing agents and molded parts, requiring good adhesion, chemical resistance and high impact strength, as well as improved flexibility and elasticity. It is suitable for all areas of use, such as joint filling in crack repair in the construction sector. Production of starting materials A Production example of polyether urethane carbamic acid aryl ester 1 Production of bifunctional polyether having a carbamic acid-(4-nonylphenyl ester) group at the terminal position Linear polypropylene glycol with an OH value of 56.1
222.3g of isophorone diisocyanate per 1000g
Add. After adding 1.2 g of dibutyltin dilaurate, the mixture is heated to 75° C. with vigorous stirring and kept at this temperature for 2.5 hours. The reaction product contains 3.4% isocyanate. 0.3 g of acetylzinc acetate and 215.7 g of a technical 4-nonyl-phenol mixture with branched nonyl groups are added to the isocyanate prepolymer cooled to 20-25°C. Heat at 50° C. for 2 hours with continued stirring. The product was then virtually free of isocyanate, with approximately 2.87% blocked
It has an NCO group. Example 2 Preparation of a trifunctional polyether having a carbamic acid (4-nonyl phenyl ester) group at the terminal position 141 g of isophorone diisocyanate is added to 1000 g of a branched trifunctional polypropylene glycol having an OH value of 35.6. Dibutyltin dilaurate 1.2
After addition of g and working up as in A, a reaction product containing 2.2% of isocyanate is obtained. 0.3 g of acetylzinc acetate and 131.1 g of a technical 4-nonyl-phenol mixture with branched nonyl groups are added to the isocyanate prepolymer cooled to 20-25°C. Further treatment as in A gives a product containing 1.95% of blocked NCO groups and practically free of isocyanate. Example 3 Example 1 except that 147.1 g of p-tert-butylphenol was used as the coupling agent.
Execute in the same manner as . Example 4 Prepolymer of difunctional polyether with TMDI Linear polypropylene glycol with OH number 56.1
1000g of TMDI [2,4,4-(2,2,4)-trimethylhexamethylene diisocyanate] 210
g and react as in Example A1. The reaction product has 3.47% isocyanate. 4-nonylphenol 215.7 as in Example A1
The corresponding carbamic acid esters are prepared using g. The product is practically free of isocyanates and has about 2.9% blocked NCO groups. Example 5 250 g of polytetrahydrofuran having a molecular weight of approximately 2000 and an OH number of 55.5 are reacted analogously to Example A1 with 54.95 g of isophorone diisocyanate.
The reaction product has an isocyanate value of 38.8. 300 g of the reaction product are reacted with 45.6 g of a technical 4-nonylphenol mixture at 50 DEG C. for 2 hours. The product is then virtually free of free isocyanate and approximately
It has 2.52% blocked NCO groups. Example 6 Isofluorone diisocyanate is added to 1000 g of a linear polyglycol with a molecular weight of about 2000 and an OH value of 55, prepared by copolymerizing propylene glycol with propylene oxide and ethylene oxide.
Add 222.3g. Dibutyltin dilaurate 1.2g
After addition, the mixture was heated to 75° C. with vigorous stirring and kept at this temperature for 2.5 hours. The reaction product had 3.4% isocyanate. 0.3 g of acetylzinc acetate and 215.7 g of a technical 4-nonyl-phenol mixture with branched nonyl groups are added to the isocyanate prepolymer cooled to 20-25°C. 50℃ with continued stirring
Heat for 2 hours. The product was then virtually free of isocyanate, with approximately 2.87% blocked
It has an NCO group. Example 7 Linear polypropylene glycol with OH value 56.1
1000g of XDI (xylylene diisocyanate)
188 g and react as in Example A1. The reaction product contains 3.53% isocyanate. The corresponding carbamic acid ester is prepared by reaction with 215.7 g of 4-nonylphenol. The product is practically free of isocyanates and has approximately 2.98% blocked NCO groups. B Production example of polyether urethaneurea amine 1 Heat 25.3 g of 1,2-diaminopropane to 70°C and add 250 g of the product produced in A1 from the dropping funnel within 6 hours, keeping the temperature at 70°C. . Excess 1,2-diaminopropane is then removed at 70 DEG C. under a vacuum of 0.1 Torr. The reaction product is
Contains amino groups corresponding to 35 mg/g of KOH (theoretical value: 36.5) Example 2 1176 g of the product prepared in A1 are added to 59.5 g of 1,2-diaminopropane, the mixture is heated to 80 °C with vigorous stirring and the Keep at temperature for 3.5 hours.
The reaction product contains amino groups corresponding to 34.7 mg/g of KOH. Example 3 Trimethylhexamethylenediamine (TMD)
26.9 g are reacted analogously to Example 2 with 250 g of the product prepared in A1. The reaction product is
Contains amino groups corresponding to 38 mg/g of KOH. Example 4 23.2 g of m-xylene diamine (XDA) are reacted as in Example 2 with 250 g of the product prepared in A1. The reaction product contains amino groups corresponding to 39 mg/g of KOH. Example 5 29 g of isophoronediamine (IPD) are reacted analogously to Example 2 with 250 g of the product prepared in A1. The reaction product contains amino groups corresponding to 39 mg/g of KOH. Example 6 p,p'-diaminodiphenylmethane (MDA)
250 g of the product prepared in A1 are added to 33.7 g, the mixture is heated to 100° C. with vigorous stirring and kept at this temperature for 16 hours, the reaction product contains amino groups corresponding to 37 mg/g of KOH. Example 7 23.4 g of 1,2-diaminopropane were reacted as in Example 1 with 340 g of the product prepared in A2. The reaction product contains amino groups corresponding to 22 mg/g of KOH. Example 8 180 g of product produced from 7.19 g of piperazine in A2
and reacted as in Example 2. The reaction product contains amino groups corresponding to 26 mg/g of KOH. Example 9 30 g of 1,2-diaminopropane are reacted analogously to example B1) with 250 g of the product prepared in example A4. The reaction product is KOH37.0mg/g (theoretical value:
Contains an amino group corresponding to 37.3). Example 10 35 g of 1,2-diaminopropane are reacted with 250 g of the product prepared in Example A7) as in Example B1). The reaction product is KOH38.0mg/g
(Contains amino groups corresponding to the theoretical value: 37.9.) Example 11 345.6 g of the product prepared in Example A5 are reacted with 30.6 g of 1,2-diaminopropane as in Example B1. The reaction product is KOH26. contains amino groups corresponding to 9 mg/g. Example 12 293.4 g of the product prepared in Example A1 are reacted with 80 g of an aminoamide containing imidazoline groups based on fatty acids and triethylenetetramine and having an amine value of 420. The reaction product is Contains amino groups corresponding to 58 mg/g of KOH.C Preparation example of an elasticized epoxide resin compound 1 Based on bisphenol A and epichlorohydrin, Ep value 0.53 and viscosity approximately 13 mPas at 25°C
85 parts by weight of an epoxide resin are diluted with 15 parts by weight of a glycidyl ether based on C-12 to C14-fatty alcohols and epichlorohydrin, having an Ep number of about 0.35 and a viscosity of about 10 mPas at 25 DEG C. To this diluted epoxide resin are added 420 parts by weight of the polyether urethaneurea amine according to Example B1 and 28 parts by weight of 2,4,6-tris-(dimethylaminomethyl)-phenol (DMP) and 1.6 parts by weight of 4-nonylphenol (NP). Add part. This epoxide resin compound is poured onto a 4 mm thick plate and cured at 23°C. Measure the increase in hardness (according to Shore hardness DIN 53505) at 23°C
Tensile strength and elongation after curing for 7 days (DIN
53455) and tear strength (DIN 53505). The cured compound is bright and transparent and hardly adheres to surfaces. Testing for each of the following examples was conducted as described in Example 1. The measured data are summarized in a table as the average value of three tests. Example 2 100 parts by weight of the epoxide mixture from Example 1 are added to
272 parts by weight of the amine from B3 and 16 parts by weight of DMP and 29 parts by weight of NP were added. Example 3 To 100 parts by weight of the epoxide resin mixture from Example 1 were added 359 parts by weight of the amine from Example B4 and 24 parts by weight of DMP and 28 parts by weight of NP. Example 4 Based on a weight ratio of 70/30 bisphenol A and bisphenol F and epichlorohydrin,
80 parts by weight of an epoxide resin with an Ep value of 0.54 and a viscosity of 7 mPas at 25°C are diluted with 20 parts by weight of dibutyl phthalate and then 30 parts by weight of the amine from Example B6 and
It was diluted with 20 parts by weight of DMP and 32 parts by weight of NP. Example 5 85 parts by weight of the epoxide resin from Example 1 were diluted with 15 parts by weight of glycidyl ether consisting of neopentyl glycol and epichlorohydrin and having an Ep value of 0.68 and a viscosity of 20 mPas at 25°C. Example B5
356 parts by weight of amine from and 24 parts by weight of DMP,
Mix 29 parts by weight of NP. Example 6 100 parts by weight of the epoxide resin mixture from Example 1 were cured with 539 parts by weight of the amine from Example B7 and 43 parts by weight of DMP and 63 parts by weight of NP. Example 7 100 parts by weight of the epoxide resin mixture from Example 5 were combined with 1062 parts by weight of the amine from Example B8 and DMP71.
parts by weight and 90 parts by weight of NP. Example 8 100 parts by weight of the epoxide resin from Example C1 is added to Example B1.
272 parts by weight of amine from isophoronediamine
4.7 parts by weight, 18.3 parts by weight of DMP and 11.4 parts by weight of NP were added. After diluting with 44 parts by weight of methylene chloride/i-propanol (1/1), the average particle size was approximately 20
It was uniformly mixed with 110 parts by weight of μm calcite filler. Example 9 100 parts by weight of the epoxide resin mixture from Example C1 were mixed with 155 parts by weight of the amine according to Example B1, 30.5 parts by weight of NP and 7 parts by weight of DMP. This is combined with an aminoamide imidazoline curing agent based on dimerized beef tallow fatty acid and diethylene triamine (amine value: approx. 280, amine equivalent: approx. 170, viscosity at 25°C: approx.
2800mPas) 58 parts by weight were added. Methylene chloride/i-propanol (1/1) 49
parts by weight and then filled with 90 parts by weight of calcite (approximately 20 μm) and 10 parts by weight of titanium dioxide-goldite. Example 10 100 parts by weight of a pigmented plastic compound as in example C8 were additionally added with 1 part by weight of hot silicic acid for thixotropy. Comparative Example 100 parts by weight of the epoxide mixture from Example 1 was added to Example A1.
was mixed with 400 parts by weight of carbamic acid aryl ester. In this, 1,2-
20 parts by weight of diaminopropane, 28 parts by weight of DMP and
A mixture consisting of 1.6 parts by weight of NP was added. The cured compound is milky and cloudy and extremely sticky on the surface.

【table】

Claims (1)

[Scope of Claims] 1. A curable plastic mixture, wherein the mixture comprises A. a polyether urethane urea amine having two or more reactive amine hydrogens per molecule; The acid aryl ester is combined with 2 at least one difunctional and/or polyfunctional amine compound, which a contains at least two reactive amine hydrogens in one molecule, or b at least one difunctional and/or polyfunctional amine compound in one molecule. (containing one reactive amine hydrogen and at least one azomethine group), and the reaction product of 1 and 2b can be prepared by subsequent hydrolysis of the azomethine group release]
and B glycidyl compounds having on average more than one epoxide group per molecule, and optionally C customary fillers, pigments, reaction accelerators, viscosity modifiers and additives. A curable plastic mixture characterized by: 2. The reaction product according to A1 above is produced from a polyalkylene polyether polyol having an average molecular weight of 400 to 10,000, and b an excess amount of difunctional or polyfunctional aliphatic and/or cycloaliphatic isocyanate. , in this case the ratio of NCO groups to OH groups is 1.5
2.5 and the resulting NCO group-containing prepolymer is further reacted with a phenol optionally substituted with c alkyl groups, in which case the PhOH/NCO ratio is approximately
A curable plastic mixture according to claim 1, characterized in that it varies between 1.0 and about 1.5. 3 The component according to A2 above is a difunctional and/or polyfunctional amine compound, that is, α General formula: R-NH-R ¹ -NH-R [wherein R is a linear chain having 1 to 4 carbon atoms or represents a branched alkyl group or a hydrogen atom, R ¹ represents an optionally substituted araliphatic or alicyclic alkyl group having 2 to 20 carbon atoms, or an alkyl group of a dimeric fatty acid diamine; /or may be interrupted by a heteroatom], and/or β General formula: R ² −(R ³ −NH−) _n −R ³ −R ² [wherein R ² is [formula] , R ³ represents -CH ₂ -CH ₂ - and/or -CH ₂ -CH ₂ -CH ₂ -, R ⁴ may be the same or different, and -
CH ₃ , -CH ₂ -CH ₃ , [formula] and m represents 1 or 2], and/or γ General formula: [In the formula, R ⁵ is a hydrogen atom or -(CH ₂ ) _k R ² (k=
2 or 3), or [Formula] (R ⁶ = - NHR or R ² , h = 0, 1, 2, 3),
X represents C or N], and/or δ is a condensation product of these amines and carboxylic acid, and amine of the formula m=1 and/or R ⁶ =
When using an amine of the formula R ² , the amino group:
The ratio of carbamic acid aryl ester groups is 1:1
and m=2 formula and amine of formula, R ⁶ =
When using an amine with the formula -NHR, the ratio of amino group to carbamic acid aryl ester group is
3. A curable plastics mixture according to claim 1, characterized in that the ratio is 1.8 to 2:1, and the amino groups are liberated by hydrolysis from the compound containing the group ^R2 .